Deodorant compositions and the methods of use



United States Patent DEODURANT CQMPGSHIGNS IVETHODS (BF USE Ann "nanHarold Kenneth Hawley, Woodlawn, and Thomas Bently common approaches tocontrolling odors have been oxidation of the odoriferous material bymeans of such oxidizingagents as sulfur dioxide, free chlorine, ozone,and

' hydrogen peroxide and masking by means of perfumes and otherpleasantly odoriferous compounds. The oxi dation method is complicatedby the corrosiveness of the oxidizing agents which makes it difiicult tostore and use them. In sufiiciently large concentrations in air, theseagents can corrode metal and are "annoying and even harmful to people.The masking method simply pollutes the air to a greater extent, and asubstantial portion of the public finds perfumes themselvesobjectionable in the concentrations needed to mask objectionable odors.The ideal material for treating odor-containing air is one that leaveslittle residue and is non-corrosive, odorless, nonstaining, non-toxic,non-irritating, and effective.

Accordingly, it is an object of this'invention to provide a pressurizeddeodorant composition for treating air containing objectionable odors.

It is another object of this invention to provide a process for treatingair containing objectionableodors.

It is a further object of this invention to provide a preferredpressurized deodorant composition, for treating air containingobjectionable odors, which will leave the treated air substantiallyodorless.

It is a still further object of this invention to provide a pressurizeddeodorant composition for treating air containing objectionable odors,which is non-toxic and noncorrosive and which leaves lit-file residue.

The pressurized deodorant compositions of this invention comprise from.about 0.3% by weight to about 15% by Weight of the composition of adeodorant material selected from the group consisting of aliphaticunsaturated hydrocarbons containing from one to three multi-bond carbonto carbon linkages, aliphatic saturated hydrocarbons, and mixturesthereof, said saturated and unsaturated hydrocarbons containing from 12to 18 carbon atoms, the balance of the composition being an aerosolpropellant capable of providing. a pressure from about 30 pounds persquare inch absolute to about 115 pounds .per square inch absolute inthe aerosol container, under either straight or branched chain,preferably the former.

Examples of suitable compounds are: dodecene; tetradecene; hexadecene;octadecene; dodecane; tetradecane; hexadecane; octadecane; oct-ene-ldimer; propylene tetraan odor of their own.

chain, there should not be more than about four branch this invention ispresumed to be odor cancellation.

ice

. 2 mer; 3,6-dimethyldecane; 2,4,5,7-tetramethyloctane; octadecyne; and1,3-tetradecadiene.

Lower homologs (C and lower) of these deodorant hydrocarbons are alsoefiective at controlling o'dors, but they have odors of their own. Thehigher homologs (C and above) are much less effective than the C Cdeodorant hydrocarbons of this invention. In the saturatedhydrocarbonseries, for instance, the compounds are relatively odorlessfrom octadecane down to and in cluding dodecane. Decane has a positiveodor of its own and octane and hexane are objectionable in this re- 1gard. On the other hand, homologs higher than octadecane (melting point-30 C.) tend to solidify, particularly under the evaporative coolingeliect of an aerosol propellant, and this solidificationminimizestheirelfectiveness in controlling odors, and may clog the valve ororifice of the aerosol container.

Branched chain structures, such as octene-l dimer and propylene tetramerare also efiective at controlling odors. Excessively branchedstructures, however, tend to have In addition to the longest carbonchains having from about one to about two carbon atoms. Structurescontaining aromatic or ring configurations have very strong naturalodors, and are therefore unac ceptable. Olfactory desensitization mayalso be induced by aromatics, e.g., it is believed that the aromatics ingasoline are responsible for its desensitization power.

The double and triple bonds in the hydrocarbons of this invention can bein the alpha position, conjugated, or otherwise, since it appears thatthe effectiveness of these compounds depends upon number of carbon atomsin the chain and not upon reactivity or location of the double or triplebond. it will be realized that a selection of the specific deodoranthydrocarbon for the compositions of this invention can be made on thebasis of considerations other than those relating to deodorization, suchas, cost, availability, odor, and amount of residue.

The deodorant hydrocarbons of this invention are very effective againsta wide variety of odois. Some of the more common odors which can becontrolled by these compounds are bathroom odors, frying odors, cabbageodors, fish odors, onion odors, ethyl mercaptan, and ciga-.

rette odors. The treated air is substantially odorless if the propellantselected is odorless and if no perfume is added to the product.

The compositions of this invention have a. very low level of toxicity,and are not irritating to the eyes, nose, or throat. They do not leave anoticeable residue or stain furniture, clothes, etc., under ordinaryusage.

The term deodorization is a broad one comprising several mechanisms forcontrolling odors. It is not limited to destruction of the odoriferousmaterials by chemical reaction, but includes control by adsorption orabsorption of the odorifero-us material, desensitization of theolfactory nerve, and odor cancellation. The latter mechanism is thephenomenon which occurs when the effects of two separate compounds, atleast one of which is odoriferous, cancel out, resulting in an apparentdestruction of the odor.

Although it is not desired to be bound by theory, the mechanism ofdeodorization for the hydrocarbons of A vapor phase chromatography studyof air treated by the compositions of this invention failed to detectany reaction products, Which seems to eliminate chemical interaction asthe mechanism for odor control. the human nose with the deodoranthydrocarbon dispersion prior to an exposure to objectionable odorsfailed to control the odors, which seems to eliminate the possibilitythat the mechanism for odor control is desensiti zation of the olfactorynerve. Positive evidence tor the Also, treatment of with thecompositions of this invention. By virtue of the fact that the deodoranthydrocarbons I of this invention are not reactive, a wider range ofperfumes, sanitizers and other minor additives, can be in-:

proposed theory of odor cancellation includes the results of a test inwhich an objectionable odor was introduced into one nostril of a subjectat the same time that a dis- .per-sion in air of the deodoranthydrocarbons'of this invention was introduced into the other nostril ofthe same subject. The odor was controlled (cancelled) as far as thesubject was concerned although the odorous air and theair containing thehydrocarbons never came in contact. i I I I .The deodorant hydrocarbonsof this invention solve many problems. Since they are extremelynon-reactive and substantially odorless, it is possible to formulate awide variety of aerosol compositions. Corrosion has always been aproblem in aerosol oans, particularly those made of metal,. as forinstance, iron, aluminum and the like. Thedeodorant hydrocarbons of thisinvention are not corrosive to metals, and therefore, permit a widerselection of materials for an aerosol container than would be possiblewith conventional oxidizing deodorizing agents. Even the morenon-reactive conventional deodorizing agents, such as strong perfumes,often require somekind of anti-oxidant to prevent corrosion anddegradation of the deodorizing agent. This is not necessary cluded intheformulation than can be included with the conventional deodorizingagents. With conventional deodorizing agents, and especially oxidizingagents, many perfumes are ruined upon prolonged storage.

The odorless nature of the deodorant hydrocarbons of p this inventionalso contributes to their utility (although cancellation of anobjectionable odor with the substitution of a less objectionable odormay be desirable in some situations). This permits the torrnulation ofan odorless product or the use of a perfume in a deodorant productwithout having to consider the effect of the odor of the deodorizingagent. Therefore, the deodorant hydrocarbons of this invention areespecially suited for use in an I aerosol whereas conventional maskingdeodorizing agents are not. These deodorant. hydrocarbons are unique incombining effective odor control, low odor, and low chemical reactivity.

The concentration range of about 0.3% to about 15% by weight of theproduct for the hydrocarbons of this invention in an aerosol is set onthe basis of performance. With lower concentrations than about 0.3%, thecost to the consumer of using the product would be prohibitivelyexpensive, since to achieve adequate performance, a relatively largeamount of the product would have to be used. With larger concentrationsthan 15%, the residue tends to become objectionable and the odor of somehydrocarbon' cornpoundsmay become noticeable. Solubility of largeconcentrations of the hydrocarbons in the propellant may also become aproblem with certain propellants such as the chloroiluoromethanes andichlorofluoroethanes.

' This concentration range is especially important based upon the normalusage of aerosol room deodorants which is about two to three grams perusage.

The aerosol propellant should be selected with care.

First it must provide the proper amount of pressure in order to achievean adequate dispersion of the active deodorant material in air. From 0to 115 pounds per square inch absolute (at about 70 C.) is preferred.Ideally, the propellant is not flammable. From this standpoint, thehalogenated hydrocarbons and inorganic propellants are preferred whereassuch propellants as N butane, isob-utane, and propane are not. However,

some halogenated hydrocarbons such as methylene chlor'id-e tendto causecorrosion in metal cans in the presence of waterwhere they-react to dormhydrochloric acidwhile N-butane, isobutane, and propane do not. Somehalogenated hydrocarbons also have odors of their own which wouldbeunacceptable in an odorless-product but which could betolerate'd insome I can also pose a toxicity problem. The inorganic prolants.

perfumed products, and some pellants such as nitrogen gas are notsuitable from the standpoint-that a single phase product is desirableand; p the deodorant hydrocarbons of this invention cannot form a singlephase with the compressed gas inorganic propel However, two phaseproducts can be used, although they may requireagitation prior to use.From the standpoints of odor, corrosiveness, chemicalinertness,flammability, and toxicity, a mixture of-trichlorofluoromethane anddichlorodifluoromethane is preferred.

if flammability is not a problem and if lower cost is desirable, thesaturated hydrocarbon propellants areuserul. Isobu-ta'ne and-N-butaneare best from the standpoint of a propervapor-pressure, but propaneand'pentane are also useful and in mixture s can provide the same vaporpressures as isobutaneand N-butane. Mixtures of these hydro-carbonpropellants with chloroand/or fluoro substi-t-uted hydrocarbons can givethe proper vapor pres,-

sure and eliminate flammability While lowering cost as I compared withthe pure chloroand/ or fluor o-substituted 7 suitable vapor pressurewhen used alone, butthey can be used in mixtures so long as the mixturehas a proper vapor pressure and the mixture is compatible.

It will be understood that the propellant must be chosen in view of thefinished product, and that suchf'considerations as odor, flammability,toxicit chemical reactivity,

corrosiveness, availability,cost, and vapor pressure of the individualpropellantwill determine whether his selected,

either aloneor as part of a mixture, for a given-product. Once asuitable propellant has been selected, the loading of the aerosolcontainer is carried out by conventional procedures which will not bedescribed here in :detail I but which may be found in PressurizedPackaging, Herska, I

A., and Pickthall 1;, chapter V, pp. 106-123, Academic Press,- Inc.'(1958). j v I i T Suitable additives to the compositions of thisinvention, but which are not necessary, include perfumes and suchanti-bacterial agents as quaternary ammonium compounds (e.g.,benzethonium chloride), propylene glycol, tr-iethylone glycol, andhalogenated hydrocarbons (e.g., hexachloro-phene). A normally solidanti-bacterial agent is preferably used with anon-volatile solvent toprevent the formation of an irritating dust when the composition issprayed into the atmosphere. I

v The following examples illustrate the practice of this invention andthe advantages which accrue from the com:

positions and process of this invention Example I The tollowing table'compares compositions comprising the various ,deodoranthydrocarbons orthis invention and certain lower homologs based upon the following testmethod. I

Ethyl mercaptan, chopped onions, and cigarette butts I were placed,respectively, in three separate one gallon jars. Suflicient odoriferousair from these jars was placed in three similar one gallon jars'tocreate odors of a su fficient strength that it took six 1 to 10dilutions (one part I of the odoriferous air plus nine partsfresh air)to reach a dilution where the odor was not detectable (threshold) in thecase of ethyl mercaptan and live such dilutions in the case of theonions and cigarettes. This odoriferous air provided the standardconcentrations of odors for this test 0.5 -gm.. of pressurizedaerosolcompositions ,convtaining 1% of the testmaterials listed belowand the tially odorfree.

balance propellant, were these-standard concentrations of odors. (Thepropellant was a 50/50 mixture of trichlonofiuoromethane anddichlorodi-fluoromethane.) The IlLlIIlbfiP-Of to dilu-' T tions with:fresh air needed to reach a 'thresholdodor for each of the jars wasthen determined. The same procedure was followed withan aerosolcontaining only propellant, which served as a blank.

sprayed into jars'containing 1-hexadecene, 1.0% denatured alcohol, 0.21%of a perfume and the rest a 50/50 mixture of trichlorofluoro- Anotherset of jars with the same three standard concentrations of odors wereinjected with 0.5 gm. samples of the aerosol composition-s until thethreshold odor was reached. This procedurewas also followed using thepropellant blank. 1 V Y Thus, in this test there were u ee numbersobtained for each compound and three. numbers for the blanks.

The first number was the sumof the number of dilutions required toreduce all three odors (standard concentrations) to a threshold level.The second number was the sum ofthe number of dilutions required toreduce all three odors to ath-reshold level after the standard odorconcentration had been treatedwith 0.5 gm. of the test material orblank. The third :figure was the sum of the number of 0.5gm.--injections of the test material or blank required to reduce thestandard odor concentration to the threshold level.

These three numbers were combined arbitrarily to give a singleperformance number which reflects the de-.

odoran-t performance of the individualoompound. The

sum of the last two numbers .of the three is subtracted .fir-om thefirst number to give this performance number.

The slight deodorization effect of the propellant is acmethane anddiehlorodifluoromethane. The product had onlythe pleasant odor of theperfume.

This composition was used on the usual home odors and was found to be aneffective deodorant.

Example I V An aerosol air deodorizzing composition was prepared with2.0% l-hex-adecene, 0.0004% pine needle oil, andthe rest a 50/ 5'0mixture of trichlorofluoromethane and t i The composition was packeddichlorodifiuoromcthane. in aconventional aerosol can. The productitself was substantially odor free to observers.

This composition was usedwith the usual home odors and found to be aneffective deodorant.

counted for by computing the performance number for the blank and thensubtracting this from the performance number of the test material togive a corrected performance number. This has the efieot of making theperformance number of the blank equal to -zero. All figores in thefollowing table are corrected performance numbers.

Compound Oct ne Decene Dodecene Tefiradet'sno Hexadecene Octadpr'smpDecane Dodecane l Theseexamples were part of the screening test androughly indicate the relative deodorant performance of some of therepresentative individual compounds of the O -C aliphatic hydrocarbonsof the compositions of this invention. The good performance numbers ofthe lower homologs are accounted for in part by the masking effect oftheir own odor.

Example II A pressurized aerosol air deodorizing composition wasprepared which contained 1.4% l-hexadecene, 1.0% denatured alcohol,0.07% lhexachlorophene, and the balance a 50/50 mixture oftrichlorofiuoromethane and dichlorodifluoromethane. The product waspacked in a conventional aerosol container. The product itself wassubstan- This product was .used on the usual cooking, cigarette andbathroom odors found in the home to provide concentrations ofl-hexadecene ranging from 0.1 to 10 p.p.m. in the air; the product wasfound to be an effective, odorless deodorant. t. i

Example Ill An aerosol air deordorizing composition, packed "in aconventional aerosol can. Was prepared containing 1.4%

Number chlorodifiuoromethane, methylene. chloride, N-butane,'

Example V An odorless aerosol air deodorizing composition was preparedwith 1.5% hexadecane, 0.5% deodorized kerosene, and the rest a50/50mixture of triohlorofluoromethane and dichlorodifluoromethane. Thecomposition was packed in a conventional aerosol can.

This composition was used with the usual home odors and was found to bean effective deodorant.

Example VI An odorless aerosol air deodorizing composition was preparedwith 3.0 gm. l hexadecene, 1.4 gm. denatured ethyl alcohol, 0.1 gm.hexachlorophene, and 136 gm. of-a 50/50 mixture oftrichlorofluoromethane and diclhlorodifluoromethane and packed in aconventional aerosol container. The product was substantially odor free.

This composition was used on the usual home odors and was found to be anefiective deodorant.

Example Vll An odorless aerosol air deodorizing composition was preparedwith 4.0% ootene-l dimer and the rest .a50/50 mixture oftr-ichlorofluor'omethane and .dichlorodifiuoromethane. The compositionwas packed in a conventional aerosol container. The product itself wassubstantially odor free.

This composition was used with the usual home odors and was found to bean effective deodorant.

All percentages in the preceding examples were by weight of the totalproduct. i

Carbon dioxide, nitrous oxide, argon, nitrogen, difluoroethane,isobutane, trichloroiiuoromethane, chlorodifiuoroethane,octafluorocyclobutane, isopentane, N-pentane, di-

propane, vinyl chloride, and mixtures of the above can be substitutedfor the propellantin the preceding ex-' ceding examples withsubstantially equivalent results.

hydrocarbons, and mixtures thereof, the balance being an aerosolpropellant capable of providing a pressurefrom What [is claimed is:

l. A pressurized deodorantcomposition comprising from about 0.3% toabout 15% by weight of the composition or a deodorant hydrocarboncontaining from 12 to 18 carbon atoms, said hydrocarbon containing notmore than about our branched chains having from about one to about twocarbon atoms, and said hydrocarbon. being selected from the groupconsisting of aliphatic on saturated hydrocarbons containing from one tothree multi-bond carbon to carbon linkages, aliphatic saturated methane;

pounds per square inchabsolute in the aerosol container under conditionsofznormal use." p 2. The compositionofclaim l in which the deodorant,hydrocarbon is a straightohain compound and the aerosol propellantisJselectedl-from the group consisting of isobutane,trichlorofluoromethane, dichlorodiiiuoromethane,

and mixtures thereof.

mixture of trichlorofluorome-thane and dichloro difiuoroa methane.

'. The composition ofclaim 1 in which the'hydrt Q.;1 ;part per millionof said air 'and in a concentration :sufficie'nt to control the odor insaid air of deodoranthy 31The composition of'clairn 1 in which thehydrocar- :b'on is hexadecane and the aerosolpropellant isv a mixture jg"o f trichlorofluoromethane and dichlorodifluorornethane.

carbon is l-hexadecene and the aerosol propellant is a.

imixtu'retof trichlorofluorornet'hane and dichlorodifluorot 6. The"composltlon of claim 5 containing a minor 4 amountof pine-needle oil.

drocarbons containingflfrom 12'to 1l8lcarbon'eitoms, said i hydrocarbonscontainingnot rnore than about iour' branched jchains having from aboutone'to; about two carbon atoms, and saidhydrocarbons being selected fromthe' group consisting of aliphatic-unsaturatedhydrocar bonscontainingfrom one to three multi-bond carbon to carbon linkages,aliphatic saturated .hydroc' iarbons, and

mixtures thereof. 8. 'T'he'pro'cess of cla' A 7 in the hydrocarbons aredispersed in ainbyjneansto f an aerosol propellant. V

Referencesfliterl in the file 'of this patent UNITED STATES PATENTS588,766 Ekenberg tAu .-24, 1897 Joy et a1. 5"

about pounds per square inch absolute to about I p t 7. The process of'deodorizing' odor containing air comprising thestep of dispersinginair, not less-than-about'

1. A PRESSURIZED DEODORANT COMPOSITION COMPRISING FROM ABOUT 0.3% TOABOUT 15% BY WEIGHT OF THE COMPOSITION OF A DEODORANT HYDROCARBONCONTAINING FROM 12 TO 18 CARBON ATOMS, SAID HYDROCARBON CONTAINING NOTMORE THAN ABOUT FOUR BRANCHES CHAINS HAVING FROM ABOUT ONE TO ABOUT TWOCARBON ATOMS, AND SAID HYDROCARBON BEING SELCTED FROM THE GROUPCONSISTING OF ALIPHATIC UNSATURATED HYDROCARBONS CONTAINING FROM ONE TOTHREE MULTI-BOND CARBON TO CARBON LINKAGES, ALIPHATIC SATURATEDHYDROCARBONS, AND MIXTURES THEREOF, THE BALANCE BEING AN AEROSOLPROPELLANT CAPABLE OF PROVIDING A PRESSURE FROM ABOUT 30 POUNDS PERSQUARE INCH ABSOLUTE TO ABOUT 115 POUNDS PER SQUARE INCH ABSOLUTE IN THEAREOSOL CONTAINIER UNDER CONDITIONS OF NORMAL USE.